JP6043870B2 - Heat medium composition for solar power generation system - Google Patents
Heat medium composition for solar power generation system Download PDFInfo
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- JP6043870B2 JP6043870B2 JP2015513914A JP2015513914A JP6043870B2 JP 6043870 B2 JP6043870 B2 JP 6043870B2 JP 2015513914 A JP2015513914 A JP 2015513914A JP 2015513914 A JP2015513914 A JP 2015513914A JP 6043870 B2 JP6043870 B2 JP 6043870B2
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- 239000013028 medium composition Substances 0.000 title claims description 33
- 238000010248 power generation Methods 0.000 title claims description 32
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 60
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 38
- -1 3-glycidoxypropyl group Chemical group 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- HTUCJWIGUOMFRO-UHFFFAOYSA-N 1-phenoxy-2,3-diphenylbenzene Chemical compound C=1C=CC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C=1OC1=CC=CC=C1 HTUCJWIGUOMFRO-UHFFFAOYSA-N 0.000 description 1
- JMCMBKXKEBELAE-UHFFFAOYSA-N 3-(3-aminopropyl-ethoxy-methylsilyl)oxybutan-1-amine Chemical compound NCCC[Si](C)(OCC)OC(C)CCN JMCMBKXKEBELAE-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、太陽熱発電システムに用いられる熱媒体組成物に関し、該熱媒体がパイプ内で分解することがなく、パイプの劣化を防止することが可能な太陽熱発電システム用熱媒体組成物に関する。 The present invention relates to a heat medium composition for use in a solar thermal power generation system, and relates to a heat medium composition for a solar thermal power generation system capable of preventing deterioration of the pipe without being decomposed in the pipe.
太陽熱発電（ＣＳＰ）システムは、太陽光を集め、熱媒体を加熱してタービンを駆動させて電力を得る発電方式である。この太陽熱発電システムの一例として、太陽光を受ける凹面鏡とその焦点部に設置された熱媒体を流通させるパイプとを備えた集光モジュールを用い、前記パイプに熱媒体を流して加熱し、この熱媒体を発電用タービンに導き、その熱エネルギーを利用してタービンを駆動させて発電するとともに、冷却された熱媒体をパイプに循環供給する構成の発電システムが知られている（例えば、特許文献１参照。）。 A solar thermal power generation (CSP) system is a power generation system that collects sunlight and heats a heat medium to drive a turbine to obtain electric power. As an example of this solar thermal power generation system, a condensing module including a concave mirror that receives sunlight and a pipe that circulates a heat medium installed at the focal point thereof is used. A power generation system having a configuration in which a medium is guided to a power generation turbine and the turbine is driven using the thermal energy to generate power and a cooled heat medium is circulated and supplied to a pipe is known (for example, Patent Document 1). reference.).
前記太陽熱発電システムに使用される熱媒体としては、ジフェニルエーテル、ジフェニルエーテル・ビフェニル混合物、ポリフェニルエーテル組成物（例えば、特許文献２〜６参照。）などが知られている。
As the heat medium used in the solar thermal power generation system, diphenyl ether, diphenyl ether / biphenyl mixture, polyphenyl ether composition (for example, see
しかしながら、ジフェニルエーテルを含む熱媒体を用いた太陽熱発電システムにあっては、熱媒体流通用のパイプ内で、パイプ内表面に露出した金属が触媒となり、ジフェニルエーテルが反応して反応生成物と水素ガスとを生じ、熱輸送流体が劣化したり、水素脆化によってパイプの強度が劣化する問題がある。 However, in a solar thermal power generation system using a heat medium containing diphenyl ether, the metal exposed on the inner surface of the pipe serves as a catalyst in the pipe for circulation of the heat medium, and the reaction product and hydrogen gas react with the reaction of diphenyl ether. There is a problem that the heat transport fluid deteriorates and the strength of the pipe deteriorates due to hydrogen embrittlement.
図１は、パイプ１内で熱媒体２中に含まれるジフェニルエーテル（Ａ）が、パイプ１内表面に露出した金属と接触することにより脱水素反応し、反応生成物（Ｂ）と水素ガス（Ｈ２）を生じた状態を示す図である。
図示のように熱媒体２から水素ガスが生じると、この水素ガスによってパイプ１が水素脆化を起こし、強度低下や破損の原因となる可能性がある。また、この反応によって生じた水素ガスや反応生成物によって熱媒体が劣化し、熱媒体による熱輸送効率が悪くなるおそれがある。
FIG. 1 shows that the diphenyl ether (A) contained in the
When hydrogen gas is generated from the
本発明は、前記事情に鑑みてなされ、熱媒体がパイプ内で分解することがなく、パイプの劣化を防止することが可能な太陽熱発電システム用熱媒体組成物の提供を課題とする。 This invention is made | formed in view of the said situation, and makes it a subject to provide the thermal-medium composition for solar thermal power generation systems which can prevent deterioration of a pipe, without a thermal medium decomposing | disassembling in a pipe.
前記課題を達成するため、本発明は、ジフェニルエーテルを含む熱媒体と、次式（１）で表されるシランカップリング剤とを含むことを特徴とする太陽熱発電システム用熱媒体組成物を提供する。 In order to achieve the object, the present invention provides a heat medium composition for a solar thermal power generation system, comprising a heat medium containing diphenyl ether and a silane coupling agent represented by the following formula (1). .
本発明の太陽熱発電システム用熱媒体組成物において、ジフェニルエーテルを含む熱媒体１００質量部に対し、前記シランカップリング剤０．１〜１０質量部を含むことが好ましい。 In the heat medium composition for a solar thermal power generation system of the present invention, it is preferable that 0.1 to 10 parts by mass of the silane coupling agent is included with respect to 100 parts by mass of the heat medium containing diphenyl ether.
本発明の太陽熱発電システム用熱媒体組成物において、前記熱媒体は、ジフェニルエーテル−ビフェニル混合物であることが好ましい。 In the heat medium composition for a solar power generation system of the present invention, the heat medium is preferably a diphenyl ether-biphenyl mixture.
また本発明は、次式（１）で表されるシランカップリング剤からなり、ジフェニルエーテルを含む熱媒体を流通させるパイプを保護するためのパイプ保護剤を提供する。 In addition, the present invention provides a pipe protecting agent for protecting a pipe made of a silane coupling agent represented by the following formula (1) and circulating a heat medium containing diphenyl ether.
本発明の太陽熱発電システム用熱媒体組成物は、シランカップリング剤がパイプ内表面に被膜を形成し、ジフェニルエーテルを含む熱媒体がパイプ内で分解することがなく、パイプの劣化を防止することができ、太陽熱発電システムの耐久性を高めることができる。 In the heat medium composition for a solar thermal power generation system of the present invention, the silane coupling agent forms a film on the inner surface of the pipe, and the heat medium containing diphenyl ether does not decompose in the pipe, thereby preventing deterioration of the pipe. The durability of the solar thermal power generation system can be increased.
本発明の太陽熱発電システム用熱媒体組成物は、ジフェニルエーテルを含む熱媒体と、次式（１）で表されるシランカップリング剤とを含むことを特徴としている。 The heat medium composition for solar thermal power generation systems of this invention is characterized by including the heat medium containing diphenyl ether and the silane coupling agent represented by following formula (1).
前記シランカップリング剤において、ＯＲ１，ＯＲ２，ＯＲ３は、アルコキシル基であればよく、特に限定されないが、メトキシ基またはエトキシ基であることが好ましい。
前記シランカップリング剤としては、１種を用いてもよいし、２種以上を用いてもよい。
本発明において、式（１）で表されるシランカップリング剤であってＸがビニル基、３−グリシドキシプロピル基及びＮ−フェニル−３−アミノプロピル基から選ばれる基であるものが好ましく、式（１）で表されるシランカップリング剤であってＸがビニル基であるものと式（１）で表されるシランカップリング剤であってＸが３−グリシドキシプロピル基であるものとの混合物がより好ましい。
In the silane coupling agent, OR 1 , OR 2 , and OR 3 are not particularly limited as long as they are alkoxyl groups, but are preferably methoxy groups or ethoxy groups.
As said silane coupling agent, 1 type may be used and 2 or more types may be used.
In the present invention, a silane coupling agent represented by the formula (1) wherein X is a group selected from a vinyl group, a 3-glycidoxypropyl group and an N-phenyl-3-aminopropyl group is preferable. A silane coupling agent represented by formula (1), wherein X is a vinyl group, and a silane coupling agent represented by formula (1), wherein X is a 3-glycidoxypropyl group Mixtures with those are more preferred.
本発明の太陽熱発電システム用熱媒体組成物において、前記シランカップリング剤の含有量は特に限定されないが、シランカップリング剤によるパイプの保護効果が十分に得られ、かつ熱媒体の粘度を低くするために、ジフェニルエーテルを含む熱媒体１００質量部に対し、シランカップリング剤０．０１〜１０質量部の範囲とすることが好ましく、０．０１〜５質量部の範囲とすることがより好ましい。 In the heat medium composition for a solar thermal power generation system of the present invention, the content of the silane coupling agent is not particularly limited. However, the pipe can be sufficiently protected by the silane coupling agent, and the viscosity of the heat medium is lowered. Therefore, it is preferable to set it as the range of 0.01-10 mass parts of silane coupling agents with respect to 100 mass parts of heat media containing diphenyl ether, and it is more preferable to set it as the range of 0.01-5 mass parts.
本発明の太陽熱発電システム用熱媒体組成物において、熱媒体としては、ジフェニルエーテル単独の熱媒体、ジフェニルエーテルと他の成分との混合物からなる熱媒体を用いることができる。ジフェニルエーテルと混合可能な他の成分としては、ビフェニル、ビフェニル誘導体、ポリフェニルエーテルなどが挙げられ、それらの中でもジフェニルエーテル−ビフェニル混合物が好ましい。ジフェニルエーテル−ビフェニル混合物を用いる場合、混合物中のビフェニル含有量は、１０〜４０質量％の範囲とすることが好ましい。 In the heat medium composition for the solar thermal power generation system of the present invention, as the heat medium, a heat medium composed of diphenyl ether alone or a mixture of diphenyl ether and other components can be used. Other components that can be mixed with diphenyl ether include biphenyl, biphenyl derivatives, polyphenyl ether, and the like, and among them, a diphenyl ether-biphenyl mixture is preferable. When a diphenyl ether-biphenyl mixture is used, the biphenyl content in the mixture is preferably in the range of 10 to 40% by mass.
本発明の太陽熱発電システム用熱媒体組成物は、必須成分である熱媒体と前記シランカップリング剤以外に、熱媒体に添加される周知の添加物を必要に応じて１種以上添加してもよい。 The heat medium composition for the solar thermal power generation system of the present invention may be added with one or more well-known additives added to the heat medium as necessary in addition to the heat medium that is an essential component and the silane coupling agent. Good.
図２は、本発明による太陽熱発電システム用熱媒体組成物を用いた場合に、パイプ１内壁に生じた被膜３によってジフェニルエーテル（Ａ）の反応を防いでいる状態を示す図である。
パイプ１内に本発明の太陽熱発電システム用熱媒体組成物２を流すと、パイプ１内壁にシランカップリング剤の被膜３が形成され、この被膜３によって熱媒体組成物２中のジフェニルエーテル（Ａ）がパイプ１内壁の金属露出面に接触することが防がれ、金属との接触によるジフェニルエーテル（Ａ）の反応とそれに伴う水素ガス発生が防止される。
FIG. 2 is a view showing a state in which the reaction of diphenyl ether (A) is prevented by the coating 3 formed on the inner wall of the pipe 1 when using the heat medium composition for the solar thermal power generation system according to the present invention.
When the
本発明の太陽熱発電システム用熱媒体組成物は、ジフェニルエーテルを含む熱媒体がパイプ内で分解することがなく、パイプの劣化を防止することができ、太陽熱発電システムの耐久性を高めることができる。 The heat medium composition for a solar thermal power generation system of the present invention can prevent the heat medium containing diphenyl ether from being decomposed in the pipe, prevent deterioration of the pipe, and enhance the durability of the solar thermal power generation system.
また本発明は、次式（１）で表されるシランカップリング剤からなり、ジフェニルエーテルを含む熱媒体を流通させるパイプを保護するためのパイプ保護剤を提供する。 In addition, the present invention provides a pipe protecting agent for protecting a pipe made of a silane coupling agent represented by the following formula (1) and circulating a heat medium containing diphenyl ether.
このパイプ保護剤は、前述した太陽熱発電システム用熱媒体組成物のように、熱媒体中に添加することによって、パイプ内表面に被膜を形成せしめ、ジフェニルエーテルを含む熱媒体がパイプ内で分解することを防止し、パイプの劣化を防止するために使用することができる。さらに、このパイプ保護剤は、単独で、或いはジフェニルエーテルを含む熱媒体以外の適当な溶媒に添加した状態でパイプ内表面に接触させることによって、該パイプ内表面に被膜を形成し、このように被膜を形成したパイプを太陽熱発電システムのパイプとして使用するためのパイプ保護剤として使用することもできる。 When this pipe protective agent is added to the heat medium as in the above-described heat medium composition for solar power generation systems, a film is formed on the inner surface of the pipe, and the heat medium containing diphenyl ether is decomposed in the pipe. Can be used to prevent pipe deterioration. Furthermore, this pipe protective agent forms a coating on the inner surface of the pipe by contacting with the inner surface of the pipe either alone or in a state where it is added to a suitable solvent other than a heat medium containing diphenyl ether. It is also possible to use the pipe formed as a pipe protective agent for use as a pipe of a solar thermal power generation system.
以下、実施例により本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.
［実施例１］
シランカップリング剤として次式（２）
[Example 1]
The following formula (2) as a silane coupling agent
で表される３−グリシドキシプロピルトリメトキシシラン（信越化学工業社製、商品名「ＫＢＭ−４０３」）を、ステンレス鋼（ＳＵＳ３０４）板の表面に塗布し、１２０℃に加熱し反応させた後、アセトンで洗浄し、乾燥させ、前記シランカップリング剤塗布部分にジフェニルエーテルを滴下し、協和界面科学社製の接触角測定器を用いて接触角を測定した。その結果を表１に記す。 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) was applied to the surface of a stainless steel (SUS304) plate and heated to 120 ° C. for reaction. Then, it wash | cleaned with acetone, it was made to dry, the diphenyl ether was dripped at the said silane coupling agent application part, and the contact angle was measured using the Kyowa Interface Science company contact angle measuring device. The results are shown in Table 1.
［実施例２］
シランカップリング剤として次式（３）
[Example 2]
The following formula (3) as a silane coupling agent
で表される３−メタクリロキシプロピルトリメトキシシラン（信越化学工業社製、商品名「ＫＢＭ−５０３」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 The contact angle was measured in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane (trade name “KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by The results are shown in Table 1.
［実施例３］
シランカップリング剤として次式（４）
[Example 3]
The following formula (4) as a silane coupling agent
で表される３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名「ＫＢＭ−９０３」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 The contact angle was measured in the same manner as in Example 1 except that 3-aminopropyltrimethoxysilane (trade name “KBM-903”, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by The results are shown in Table 1.
［実施例４］
シランカップリング剤として次式（５）
[Example 4]
As a silane coupling agent, the following formula (5)
で表されるＮ−フェニル−３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名「ＫＢＭ−５７３」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 The contact angle was measured in the same manner as in Example 1 except that N-phenyl-3-aminopropyltrimethoxysilane (trade name “KBM-573”, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by The results are shown in Table 1.
［実施例５］
シランカップリング剤として次式（６）
[Example 5]
The following formula (6) as a silane coupling agent
で表される３−メタクリロキシプロピルトリエトキシシラン（信越化学工業社製、商品名「ＫＢＥ−５０３」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 The contact angle was measured in the same manner as in Example 1 except that 3-methacryloxypropyltriethoxysilane (trade name “KBE-503” manufactured by Shin-Etsu Chemical Co., Ltd.) represented by The results are shown in Table 1.
［実施例６］
シランカップリング剤として次式（７）
[Example 6]
As a silane coupling agent, the following formula (7)
で表されるＮ−２（アミノエチル）３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名「ＫＢＭ−５０３」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (trade name “KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by It was measured. The results are shown in Table 1.
［比較例１］
シランカップリング剤を用いず、アセトン洗浄したステンレス鋼板の表面に直接ジフェニルエーテルを滴下し、接触角を測定した。その結果を表１に記す。
[Comparative Example 1]
Without using a silane coupling agent, diphenyl ether was dropped directly on the surface of the stainless steel plate washed with acetone, and the contact angle was measured. The results are shown in Table 1.
［比較例２］
シランカップリング剤として次式（８）
[Comparative Example 2]
The following formula (8) as a silane coupling agent
で表される３−メタクリロキシプロピルメチルジメトキシシラン（信越化学工業社製、商品名「ＫＢＭ−５０２」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 The contact angle was measured in the same manner as in Example 1 except that 3-methacryloxypropylmethyldimethoxysilane (trade name “KBM-502” manufactured by Shin-Etsu Chemical Co., Ltd.) represented by The results are shown in Table 1.
［比較例３］
シランカップリング剤として次式（９）
[Comparative Example 3]
As a silane coupling agent, the following formula (9)
で表される３−メタクリロキシプロピルメチルジエトキシシラン（信越化学工業社製、商品名「ＫＢＥ−５０２」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 The contact angle was measured in the same manner as in Example 1 except that 3-methacryloxypropylmethyldiethoxysilane (trade name “KBE-502” manufactured by Shin-Etsu Chemical Co., Ltd.) represented by The results are shown in Table 1.
［比較例４］
シランカップリング剤として次式（１０）
[Comparative Example 4]
The following formula (10) as a silane coupling agent
で表されるＮ−２（アミノエチル）３−アミノプロピルメチルジエトキシシラン（信越化学工業社製、商品名「ＫＢＭ−６０２」）を用い、それ以外は実施例１と同様にして、接触角を測定した。その結果を表１に記す。 N-2 (aminoethyl) 3-aminopropylmethyldiethoxysilane (trade name “KBM-602”, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by Was measured. The results are shown in Table 1.
表１の結果から、本発明に係る実施例１〜４のシランカップリング剤をステンレス鋼板に塗布した場合、シランカップリング剤を使用していない比較例１と比べて接触角が減少した。これは、被膜が形成されたことでジフェニルエーテルが金属表面に接触し難くなっていることを示している。
一方、アルコキシル基が２つである比較例２〜４のシランカップリング剤は、接触角が比較例１と同程度であった。
From the result of Table 1, when the silane coupling agent of Examples 1-4 which concerns on this invention was apply | coated to the stainless steel plate, the contact angle decreased compared with the comparative example 1 which is not using the silane coupling agent. This indicates that the formation of the coating makes it difficult for the diphenyl ether to contact the metal surface.
On the other hand, the contact angles of the silane coupling agents of Comparative Examples 2 to 4 having two alkoxyl groups were the same as those of Comparative Example 1.
シランカップリング剤を用いて、熱媒油（組成：０．０２ｗｔ％−９．９８ｗｔ％のジフェニル−ジフェニルエーテル共結晶）を調製した。各サンプルをるつぼに滴下し、加熱炉で最大温度４００℃〜４５０℃まで約３０分加熱した。 Heat transfer oil (composition: 0.02 wt% -9.98 wt% diphenyl-diphenyl ether co-crystal) was prepared using a silane coupling agent. Each sample was dropped into a crucible and heated in a heating furnace to a maximum temperature of 400 ° C to 450 ° C for about 30 minutes.
熱安定性の検討の結果、比較により、分解は純粋な共結晶混合物（約３７０℃）より５℃高い約３７５℃から始まることが確認された。 As a result of thermal stability studies, the comparison confirmed that the decomposition began at about 375 ° C., 5 ° C. higher than the pure co-crystal mixture (about 370 ° C.).
［実施例７〜９、比較例５］
表２に示す成分を混合し、熱媒体組成物を得た。
[Examples 7 to 9, Comparative Example 5]
The components shown in Table 2 were mixed to obtain a heat medium composition.
表２中、各略号は以下の意味を有する。また、［ ］内の数値は各成分の量（モル％）を表す。
（２）：前記式（２）で表される３−グリシドキシプロピルトリメトキシシラン（商品名：ＫＢＭ−４０３、信越化学社製）。
（５）：前記式（５）で表されるＮ−フェニル−３−アミノプロピルトリメトキシシラン（商品名：ＫＢＭ−５７３、信越化学社製）。
（１１）：下記式（１１）で表されるビニルトリメトキシシラン（商品名：ＫＢＭ−１００３、信越化学社製）。
ＤＰＯ／ＢＰ：ジフェニルエーテルとビフェニルとの混合物（ビフェニル含有量：２７ｗｔ％）（ダウ社製）。
In Table 2, each abbreviation has the following meaning. Moreover, the numerical value in [] represents the quantity (mol%) of each component.
(2): 3-glycidoxypropyltrimethoxysilane represented by the above formula (2) (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
(5): N-phenyl-3-aminopropyltrimethoxysilane represented by the above formula (5) (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.).
(11): Vinyltrimethoxysilane represented by the following formula (11) (trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.).
DPO / BP: A mixture of diphenyl ether and biphenyl (biphenyl content: 27 wt%) (manufactured by Dow).
［熱分解評価（１）］
実施例７〜９及び比較例５の各熱媒体組成物５０ｇを試料容器に入れた。次いで、試料容器をオーブンに入れ、４００℃又は４２５℃で２０日間加熱した。その後、熱媒体組成物についてガスクロマトグラフィー分析（液相分析）を行い、分解化学物質の量（ｗｔ％）を評価した。結果を図３に示す。
[Pyrolysis evaluation (1)]
50 g of each heat carrier composition of Examples 7 to 9 and Comparative Example 5 was placed in a sample container. The sample container was then placed in an oven and heated at 400 ° C. or 425 ° C. for 20 days. Thereafter, gas chromatographic analysis (liquid phase analysis) was performed on the heat medium composition, and the amount (wt%) of the decomposition chemical substance was evaluated. The results are shown in FIG.
図３に示される結果より、４００℃で加熱後、実施例８及び比較例５の熱媒体組成物においては分解化学物質の量はほぼ同等であり、実施例７及び９の熱媒体組成物においては更に少なかった。４２５℃で加熱後、実施例７〜９の熱媒体組成物は、比較例５の熱媒体組成物と比べて分解化学物質の量が抑制されていた。特に、ビニル基を有するシランカップリング剤を含む実施例９の熱媒体組成物においては、４２５℃で加熱後の分解化学物質の量が、４００℃で加熱後の分解化学物質の量と比べてほとんど増えていなかった。 From the results shown in FIG. 3, after heating at 400 ° C., the amounts of decomposition chemicals in the heat medium compositions of Example 8 and Comparative Example 5 are almost the same, and in the heat medium compositions of Examples 7 and 9 Was even less. After heating at 425 ° C., the amount of decomposition chemicals in the heat medium compositions of Examples 7 to 9 was suppressed as compared with the heat medium composition of Comparative Example 5. In particular, in the heat medium composition of Example 9 including a silane coupling agent having a vinyl group, the amount of the decomposition chemical after heating at 425 ° C. is compared with the amount of the decomposition chemical after heating at 400 ° C. It has hardly increased.
［実施例１０〜１３］
表３に示す成分を混合し、熱媒体組成物を得た。
[Examples 10 to 13]
The components shown in Table 3 were mixed to obtain a heat medium composition.
表３中、各略号は前記で定義した通りである。また、［ ］内の数値は各成分の量（ｗｔ％）を表す。 In Table 3, each abbreviation is as defined above. Moreover, the numerical value in [] represents the quantity (wt%) of each component.
［熱分解評価（２）］
実施例１０〜１３の各熱媒体組成物２０ｇをステンレススチール板（ＳＵＳ３０４）の表面上に塗布し、４００℃で３時間、初期圧力１０ｂａｒで加熱した。その後、熱媒体組成物についてガスクロマトグラフィー分析を行い、ジベンゾフラン濃度（ｐｐｍ）を評価した。結果を表３に示す。
[Pyrolysis evaluation (2)]
20 g of each heat medium composition of Examples 10 to 13 was applied on the surface of a stainless steel plate (SUS304) and heated at 400 ° C. for 3 hours at an initial pressure of 10 bar. Then, the gas chromatography analysis was performed about the heat carrier composition, and the dibenzofuran density | concentration (ppm) was evaluated. The results are shown in Table 3.
表３に示される結果より、ビニル結合を０．２ｗｔ％含有するシランカップリング剤を含む実施例１１の熱媒体組成物は、ジベンゾフラン濃度を大幅に低減できることが確認された。また、ビニル基を有するシランカップリング剤と３−グリシドキシプロピル基を有するシランカップリング剤との組み合わせを用いることにより、ジベンゾフラン濃度を更に低減できることが確認された。 From the results shown in Table 3, it was confirmed that the heat medium composition of Example 11 containing a silane coupling agent containing 0.2 wt% of vinyl bonds can greatly reduce the dibenzofuran concentration. Moreover, it was confirmed that the dibenzofuran concentration can be further reduced by using a combination of a silane coupling agent having a vinyl group and a silane coupling agent having a 3-glycidoxypropyl group.
［膜形成評価（１）］
実施例１３の熱媒体組成物２０ｇをステンレススチール板（ＳＵＳ３０４）の表面上に塗布し、表４に示す温度で２時間、初期圧力１０ｂａｒで加熱した。その後、熱媒体組成物についてＸＰＳ分析を行い、形成された膜のＳｉ：Ｏ比及びＳｉ濃度を評価した。結果を表４に示す。
[Film Formation Evaluation (1)]
20 g of the heat medium composition of Example 13 was applied on the surface of a stainless steel plate (SUS304), and heated at the temperature shown in Table 4 for 2 hours at an initial pressure of 10 bar. Thereafter, XPS analysis was performed on the heat medium composition to evaluate the Si: O ratio and Si concentration of the formed film. The results are shown in Table 4.
表４に示される結果より、確実に膜が形成できることが確認された。 From the results shown in Table 4, it was confirmed that the film could be formed reliably.
本発明の太陽熱発電システム用熱媒体組成物は、太陽熱発電システム（ＣＳＰ）に用いられる熱媒体組成物に関し、該熱媒体がパイプ内で分解することがなく、パイプの劣化を防止することが可能な太陽熱発電システム用熱媒体組成物に関する。 The heat medium composition for a solar thermal power generation system according to the present invention relates to a heat medium composition used for a solar thermal power generation system (CSP), and the heat medium is not decomposed in a pipe and can prevent deterioration of the pipe. The present invention relates to a heat medium composition for a solar thermal power generation system.
以上、本発明の好ましい実施例を説明したが、本発明はこれら実施例に限定されることはない。本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。本発明は前述した説明によって限定されることはなく、添付のクレームの範囲によってのみ限定される。 The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention. The present invention is not limited by the above description, but only by the scope of the appended claims.
１…パイプ、２…熱媒体、３…被膜。 1 ... pipe, 2 ... heat medium, 3 ... coating.
Claims (4)
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| US201261701311P | 2012-09-14 | 2012-09-14 | |
| US61/701,311 | 2012-09-14 | ||
| PCT/JP2013/075394 WO2014042289A1 (en) | 2012-09-14 | 2013-09-13 | Heating medium composition for solar thermal power generation system |
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| RU2656666C1 (en) * | 2016-07-20 | 2018-06-06 | федеральное государственное бюджетное образовательное учреждение высшего образования "Самарский государственный технический университет" | Heat carrier |
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| GB1053062A (en) | 1963-04-30 | |||
| JPS6463889A (en) | 1987-09-03 | 1989-03-09 | Sharp Kk | World time-piece |
| JPH0163889U (en) * | 1987-10-20 | 1989-04-24 | ||
| BR8900832A (en) * | 1988-02-24 | 1989-10-17 | Monsanto Co | HEAT TRANSFER FLUID, SOLAR ENERGY COLLECTION PROCESS, FLUID IMPURETING REDUCTION PROCESS AND REMOVAL PROCESS OF A LESS IMPURSE PROPORTION OF A TERPHENYL ISOMER |
| US5075022A (en) | 1988-02-24 | 1991-12-24 | Monsanto Company | Heat transfer fluids |
| JPH059465A (en) * | 1991-06-28 | 1993-01-19 | Nippon Steel Chem Co Ltd | Heating medidum composition |
| JP2004143383A (en) | 2002-10-28 | 2004-05-20 | Nikko Materials Co Ltd | Solid silane-coupling agent composition, method for producing the same and resin composition containing the same |
| CA2578970A1 (en) * | 2004-09-08 | 2006-03-16 | Honeywell International Inc. | Corrosion inhibitors, corrosion inhibiting heat transfer fluids, and the use thereof |
| US8039049B2 (en) * | 2005-09-30 | 2011-10-18 | Tokyo Electron Limited | Treatment of low dielectric constant films using a batch processing system |
| US8322333B2 (en) | 2009-04-01 | 2012-12-04 | Abengoa Solar Inc. | Torque transfer between trough collector modules |
| CN101906287B (en) * | 2009-06-03 | 2014-01-22 | 淄博大运特工程材料科技有限公司 | Light-heat transformation working medium composition |
| KR101333704B1 (en) * | 2009-12-29 | 2013-11-27 | 제일모직주식회사 | Positive type photosensitive resin composition |
| US8703665B2 (en) | 2010-01-12 | 2014-04-22 | Vanderbilt University | Materials comprising deaggregated diamond nanoparticles |
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| CN104812867A (en) | 2015-07-29 |
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